WO2022210799A1 - Empilement de substrats, capteur d'image et procédé de fabrication d'un empilement de substrats - Google Patents

Empilement de substrats, capteur d'image et procédé de fabrication d'un empilement de substrats Download PDF

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Publication number
WO2022210799A1
WO2022210799A1 PCT/JP2022/015716 JP2022015716W WO2022210799A1 WO 2022210799 A1 WO2022210799 A1 WO 2022210799A1 JP 2022015716 W JP2022015716 W JP 2022015716W WO 2022210799 A1 WO2022210799 A1 WO 2022210799A1
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Prior art keywords
substrate
layer
group
compound
laminate according
Prior art date
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PCT/JP2022/015716
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English (en)
Japanese (ja)
Inventor
悠太 齋藤
歩 小川
大希 木下
Original Assignee
株式会社カネカ
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Application filed by 株式会社カネカ filed Critical 株式会社カネカ
Priority to JP2023511435A priority Critical patent/JPWO2022210799A1/ja
Priority to CN202280024560.3A priority patent/CN117083706A/zh
Publication of WO2022210799A1 publication Critical patent/WO2022210799A1/fr
Priority to US18/461,427 priority patent/US20230408923A1/en

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/075Silicon-containing compounds
    • G03F7/0757Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B38/0004Cutting, tearing or severing, e.g. bursting; Cutter details
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/02Containers; Seals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/02Containers; Seals
    • H01L23/06Containers; Seals characterised by the material of the container or its electrical properties
    • H01L23/08Containers; Seals characterised by the material of the container or its electrical properties the material being an electrical insulator, e.g. glass
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144Devices controlled by radiation
    • H01L27/146Imager structures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243Coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/26Polymeric coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00Condition, form or state of the layers or laminate
    • B32B2305/74Partially cured
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54Yield strength; Tensile strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542Shear strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/30Aspects of methods for coating glass not covered above
    • C03C2218/32After-treatment
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/30Aspects of methods for coating glass not covered above
    • C03C2218/32After-treatment
    • C03C2218/328Partly or completely removing a coating
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/30Aspects of methods for coating glass not covered above
    • C03C2218/34Masking
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00Presence of epoxy resin

Definitions

  • the present invention relates to a substrate laminate, an image sensor, and a method for manufacturing the substrate laminate.
  • Image sensors such as CMOS sensors and CCD sensors are used in digital cameras, smartphones, etc.
  • the amount used has increased, and there has been an increase in miniaturization and higher resolution. increasingly demanded.
  • a substrate laminate that constitutes an image sensor has, for example, a hollow structure in which a semiconductor element substrate having a light receiving element and a glass substrate are bonded together via a patterned layer.
  • a substrate laminate having a hollow structure is obtained by the following procedure.
  • a coating film is formed on a first substrate (for example, a glass substrate) by applying a photosensitive composition to one surface of the first substrate.
  • a photosensitive composition for example, a photosensitive composition
  • an exposed portion and a non-exposed portion composed of the semi-cured photosensitive composition are formed in the coating film.
  • a patterned semi-cured coating film (hereinafter sometimes referred to as "pattern film”) is formed on the first substrate.
  • the pattern film is cured to separate the first substrate and the second substrate. to glue.
  • Patent Document 1 The technology described in Patent Document 1 has room for improvement in terms of suppressing the contamination of foreign matter while increasing the adhesiveness between substrates.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a substrate laminate that is excellent in adhesion between substrates and is resistant to contamination by foreign matter, a method for manufacturing the same, and an image sensor having the substrate laminate. is to provide
  • a method for manufacturing a substrate laminate according to the present invention includes a process Sa, a process Sb, a process Sc, a process Sd, and a process Se.
  • a coating film is formed on one surface of the first substrate by applying a photosensitive composition to the one surface.
  • the step Sb by irradiating the coating film with an active energy ray through a photomask, an exposed portion composed of the semi-cured photosensitive composition and a non-exposed portion are formed in the coating film.
  • the patterned coating film is formed on the first substrate by removing the non-exposed portion from the first substrate with an alkaline developer.
  • step Sd the patterned coating film is heated to further cure the semi-cured photosensitive composition, thereby obtaining a first layer composed of a patterned cured product.
  • the adhesive is cured to form a second layer for bonding the first layer and the second substrate.
  • the photosensitive composition contains a curable compound having a cationic polymerizable group and a photocationic polymerization initiator, and has alkali solubility.
  • the reaction rate of the curable compound in the first layer before the step Se is 90% or more.
  • the method for manufacturing a substrate laminate after the step Sd and before the step Se, by dicing the laminate of the first substrate and the first layer, individual substrates are obtained.
  • the method further includes a step Sf1 of obtaining a laminate that has been separated into pieces, and in the step Se, the first layer of the laminate that has been separated into pieces and the second substrate are pasted together via the adhesive.
  • a laminate in which the first substrate, the first layer, the second layer and the second substrate are laminated in this order is laminated in this order. It further includes a step Sf2 of obtaining individualized laminates by dicing.
  • the alkaline developer contains an alkaline component, and the content of the alkaline component in the first layer before the step Se is 1000 ppm or less.
  • the softening point of the first layer before the step Se is 100°C or higher.
  • the elastic modulus of the first layer before the step Se measured by a nanoindentation test method at a temperature of 100° C. is 1500 N/mm 2 or more. .
  • a substrate laminate according to the present invention has a first substrate, a second substrate, and a cured material layer that bonds the first substrate and the second substrate.
  • the cured product layer has, from the first substrate side, a first layer composed of a cured photosensitive composition and a second layer composed of a cured adhesive in this order.
  • the first layer is patterned.
  • the photosensitive composition contains a curable compound having a cationic polymerizable group and a photocationic polymerization initiator, and has alkali solubility.
  • the wall surface of the second layer is curved.
  • the cured material layer further has a coating layer covering at least a part of the wall surface of the first layer, and the coating layer and the second layer are integrated is formed
  • either one of the first substrate and the second substrate is a transparent substrate.
  • one of the first substrate and the second substrate is a transparent substrate, and the other is a semiconductor element substrate.
  • the cationic polymerizable group is one or more selected from the group consisting of glycidyl groups and alicyclic epoxy groups.
  • the first substrate is a glass substrate.
  • the adhesive is an epoxy adhesive.
  • the curable compound is a polysiloxane compound.
  • the polysiloxane compound includes a monovalent organic group represented by the following chemical formula (X1), a divalent organic group represented by the following chemical formula (X2), phenol It further has one or more alkali-soluble groups selected from the group consisting of functional hydroxyl groups and carboxy groups.
  • the first layer has a height of 30 ⁇ m or more.
  • a substrate laminate according to one embodiment of the present invention is a hollow structural body having a hollow portion between the first substrate and the second substrate.
  • An image sensor according to the present invention includes the substrate laminate according to the present invention.
  • the present invention it is possible to provide a substrate laminate that has excellent adhesion between substrates and is less likely to be contaminated with foreign matter, a method for manufacturing the same, and an image sensor having the substrate laminate.
  • FIG. 4 is a partial cross-sectional view showing another example of the substrate laminate according to the present invention.
  • FIG. 4 is a partial cross-sectional view showing another example of the substrate laminate according to the present invention.
  • FIG. 4 is a partial cross-sectional view showing another example of the substrate laminate according to the present invention;
  • FIG. 4 is a partial cross-sectional view showing another example of the substrate laminate according to the present invention;
  • FIG. 4 is a plan view showing the first substrate after forming the first layer when manufacturing an example of the substrate laminate according to the present invention.
  • 1A, 1B, and 1C are cross-sectional views showing steps of an example of a method for manufacturing a substrate laminate according to the present invention.
  • FIG. 1A, 1B, and 1C are cross-sectional views showing steps of an example of a method for manufacturing a substrate laminate according to the present invention.
  • FIG. 4 is a plan view showing the first substrate after singulation when manufacturing an example of the substrate laminate according to the present invention.
  • a “photopolymerization initiator” refers to a compound that generates active species (specifically, radicals, cations, anions, etc.) upon exposure to active energy rays.
  • the term “photocationic polymerization initiator” refers to a compound that generates cations (acids) as active species upon irradiation with active energy rays.
  • a “radical photopolymerization initiator” refers to a compound that generates radicals as active species upon irradiation with active energy rays.
  • Active energy rays include visible light, ultraviolet rays, infrared rays, electron beams, X-rays, ⁇ rays, ⁇ rays, ⁇ rays, and the like.
  • a "cationic polymerizable group” refers to a functional group that polymerizes in a chain in the presence of a cation.
  • alkali-soluble group refers to a functional group that enhances solubility in alkaline solutions by interacting or reacting with alkali.
  • the photosensitive composition has alkali solubility means that the photosensitive composition contains a compound having an alkali solubility group.
  • alicyclic epoxy group refers to a functional group formed by bonding one oxygen atom to two adjacent carbon atoms among the carbon atoms constituting an alicyclic structure. , 4-epoxycyclohexyl group and the like.
  • a “polysiloxane compound” is a compound having a polysiloxane structure composed of siloxane units (Si—O—Si).
  • the polysiloxane structure includes a chain polysiloxane structure (specifically, a linear polysiloxane structure, a branched polysiloxane structure, etc.) and a cyclic polysiloxane structure.
  • epoxy-based adhesive refers to an adhesive containing a compound having an epoxy group (for example, a compound containing at least two epoxy groups in one molecule) as a main ingredient.
  • a “semi-cured state” refers to a state in which the degree of curing can be further increased by a subsequent step (for example, a heating step).
  • Solid content is a non-volatile component in the composition
  • total solid content means the total amount of constituent components of the composition excluding the solvent.
  • the "main component" of a material means the component that is contained in the material in the largest amount on a mass basis.
  • system may be added after the name of the compound to generically refer to the compound and its derivatives.
  • name of a polymer when the name of a polymer is expressed by adding "system” to the name of a compound, it means that the repeating unit of the polymer is derived from the compound or its derivative.
  • acryl and methacryl may be collectively referred to as "(meth)acryl”.
  • acrylates and methacrylates may be collectively referred to as "(meth)acrylates”.
  • a method for manufacturing a substrate laminate according to the first embodiment of the present invention includes a process Sa, a process Sb, a process Sc, a process Sd, and a process Se.
  • step Sa a coating film is formed on one surface of the first substrate by applying a photosensitive composition to one surface.
  • step Sb the coating film is irradiated with active energy rays through a photomask to form an exposed portion and a non-exposed portion composed of the semi-cured photosensitive composition in the coating film.
  • a patterned coating film is formed on the first substrate by removing the non-exposed portions from the first substrate with an alkaline developer.
  • step Sd the patterned coating film is heated to further cure the semi-cured photosensitive composition, thereby obtaining the first layer composed of the patterned cured product.
  • step Se after bonding the first layer and the second substrate with an adhesive, the adhesive is cured to obtain a second layer bonding the first layer and the second substrate.
  • the photosensitive composition contains a curable compound having a cationic polymerizable group and a photocationic polymerization initiator, and has alkali solubility.
  • the reaction rate of the curable compound in the first layer before step Se is 90% or more.
  • reaction rate the reaction rate of the curable compound in the first layer before step Se
  • reaction rate the reaction rate of the curable compound in the first layer before step Se
  • the method for measuring the reaction rate is the same method as in Examples described later or a method based thereon.
  • step Sd the patterned coating film is heated to further cure the semi-cured photosensitive composition, thereby forming a patterned cured product.
  • the first layer and the second substrate, to which foreign substances are relatively difficult to adhere are bonded together via an adhesive. Therefore, according to the manufacturing method of the board
  • step Sb since a photosensitive composition containing a curable compound having a cationic polymerizable group and a photocationic polymerization initiator is used, in step Sb, light By cationic polymerization, an exposed portion composed of a semi-cured photosensitive composition can be formed.
  • the semi-cured exposed portion obtained by photocationic polymerization has relatively high adhesion to the first substrate. Therefore, according to the method for manufacturing a substrate laminate according to the first embodiment, it is possible to enhance the adhesiveness between the substrates.
  • the reaction rate is preferably 95% or more, more preferably 97% or more, and more preferably 99% or more in order to further suppress foreign matter from entering the substrate laminate. is more preferable.
  • the upper limit of the reaction rate is not particularly limited, and may be 100%.
  • the reaction rate is, for example, the type of the curable compound, the type of the photocationic polymerization initiator, the amount of the photocationic polymerization initiator with respect to the curable compound, and the exposure conditions (specifically, the integrated exposure amount etc.) At least one of can be adjusted by changing
  • the laminate of the first substrate and the first layer is diced into individual laminates. It may further comprise a step Sf1 of obtaining
  • the manufacturing method of the substrate laminate according to the first embodiment further includes the step Sf1, in the step Se, the first layer of the separated laminate and the second substrate are bonded together via an adhesive.
  • step Se by dicing the laminate in which the first substrate, the first layer, the second layer and the second substrate are laminated in this order, individual pieces are obtained.
  • a step Sf2 of obtaining a laminated laminate may be further included.
  • FIG. 1 is a cross-sectional view showing an example of a substrate laminate obtained by the manufacturing method according to the first embodiment.
  • a substrate laminate 10 shown in FIG. 1 has a first substrate 11 , a second substrate 12 , and a cured material layer 13 that bonds the first substrate 11 and the second substrate 12 .
  • the cured product layer 13 has, from the first substrate 11 side, a first layer 131 composed of a cured photosensitive composition and a second layer 132 composed of a cured adhesive in this order.
  • the first layer 131 is patterned.
  • the photosensitive composition which is the constituent material of the first layer 131, contains a curable compound having a cationic polymerizable group and a photocationic polymerization initiator, and has alkali solubility.
  • the width of the first substrate 11 and the width of the second substrate 12 are substantially the same. may be different.
  • the substrate laminate 10 is a hollow structure having a hollow portion Z surrounded by the first substrate 11, the second substrate 12, and the cured material layer 13.
  • the hollow part Z may be a closed space.
  • the cured material layer 13 functions as a partition to prevent entry of moisture and dust into the effective pixel area.
  • the second layer 132 can be obtained, for example, by curing the adhesive with heat or ultraviolet rays, without going through the process of patterning by photolithography.
  • the volume of the adhesive usually decreases during curing (cures and shrinks), but the adhesive near the interface with the first layer 131 and near the interface with the second substrate 12 is fixed to the adjacent layers. Therefore, the wall surface of the second layer 132 obtained by curing the adhesive is generally curved as shown in FIG.
  • the first layer 131 is a layer obtained by heating the patterned coating film to further cure the semi-cured photosensitive composition in step Sd, as will be described later. Since the first layer 131 is not fixed at its end surface (the surface opposite to the first substrate 11 side) in the curing step, the wall surface of the first layer 131 is generally flat.
  • the second layer 132 formed in a state in which the curing of the adhesive has progressed (a state in which curing shrinkage has progressed).
  • the wall surface of the second layer 132 has a small degree of recession (small cure shrinkage).
  • the index of the degree of depression of the wall surface of the second layer 132 will be described below.
  • the wall surface of the second layer 132 is most It can be said that the degree of depression of the wall surface of the second layer 132 is greater as the shortest distance D to the depressed portion 132c is greater.
  • the shortest distance D the shortest distance from a straight line passing through both ends of the wall surface of the second layer in the height direction to the most recessed portion of the wall surface of the second layer.
  • the shortest distance D is preferably 0.5 ⁇ m or more and 100 ⁇ m or less, and 0.5 ⁇ m or more. It is more preferably 80 ⁇ m or less, still more preferably 1 ⁇ m or more and 50 ⁇ m or less, even more preferably 1 ⁇ m or more and 20 ⁇ m or less, and particularly preferably 1 ⁇ m or more and 10 ⁇ m or less.
  • the shortest distance D can be adjusted, for example, by changing at least one of the type of adhesive used and the curing conditions of the adhesive (heating conditions, ultraviolet irradiation conditions, etc.).
  • the cross-sectional shape of the second layer 132 is not limited to the shape shown in FIG.
  • the cross-sectional shape may be such that the width of the surface on the second substrate 12 side is larger than the width of the surface on the first layer 131 side.
  • the cross-sectional shape may be such that the width of the surface on the first layer 131 side is larger than the width of the surface on the second substrate 12 side.
  • the cured material layer 13 may further have a coating layer 133 that covers the wall surface 131a of the first layer 131.
  • the coating layer 133 and the second layer 132 are integrally formed.
  • the cured material layer 13 further has a coating layer 133 covering the wall surface 131a of the first layer 131, and the coating layer 133 and the second layer 132 are integrally formed, as evaluated by a thermal shock test. It is possible to obtain a substrate laminate having excellent reliability. In order to obtain a substrate laminate with excellent reliability evaluated by a thermal shock test, the thickness of the coating layer 133 (height from the wall surface 131a of the first layer 131) should be 0.1 ⁇ m or more and 1000 ⁇ m or less.
  • the coating layer 133 and the second layer 132 for example, at least part of the wall surface 131a of the first layer 131 and the end surface of the first layer 131 (first substrate 11 side), and then bond the first layer 131 and the second substrate 12 together via the adhesive, followed by curing the adhesive.
  • the coating layer 133 and the second layer 132 are integrally formed, in this specification, in a cross section ( FIG. 3 ) of the cured material layer 13 in the width direction, With a line BL passing through the corner 131b and parallel to the surface 12a of the second substrate 12 on the first substrate 11 side as a reference, the first substrate 11 side is the covering layer 133, and the second substrate 12 side is the second layer 132.
  • a boundary line (line BL) is shown in FIG. and the second layer 132 cannot be confirmed. That is, "the coating layer 133 and the second layer 132 are integrally formed" means that the coating layer 133 and the second layer 132 are in contact with each other in a state where the boundary cannot be confirmed in the electron microscope image. means that
  • the coating layer 133 does not have to cover the entire surface of the wall surface 131a of the first layer 131.
  • a covering layer 133 may cover a portion of the wall surface 131a of the first layer 131.
  • the reliability evaluated by the thermal shock test is excellent.
  • a substrate laminate can be obtained.
  • the height of the coating layer 133 is preferably 1 ⁇ m or more.
  • FIG. 5 to be referred to is a plan view showing the first substrate after formation of the first layer when manufacturing an example of the substrate laminate according to the first embodiment.
  • 6A to 6C and 7A to 7C to be referred to are cross-sectional views showing steps of an example of the method for manufacturing the substrate laminate according to the first embodiment.
  • the first layer 131 is formed on the large-sized first substrate 11 in a state of being patterned into a large number of square cylinders (FIG. 5).
  • the pattern of the first layer 131 is not limited to the pattern shown in FIG. 5, and may be designed in accordance with the desired shape, and may be, for example, a lattice shape.
  • the patterned first layer 131 shown in FIG. 5 can be formed by steps Sa to Sd detailed below.
  • step Sa a photosensitive composition is applied to one surface of the large-sized first substrate 11 to form a coating film 300 made of the photosensitive composition on one surface of the first substrate 11 (FIG. 6A).
  • the coating method in this case is not particularly limited, and for example, general coating methods such as spin coating, slit coating, roll coating, printing, and bar coating can be used.
  • the thickness of the coating film 300 is, for example, 0.05 ⁇ m or more and 1000 ⁇ m or less, preferably 0.1 ⁇ m or more and 500 ⁇ m or less, and more preferably 1 ⁇ m or more and 300 ⁇ m or less.
  • the coating film 300 may be heated to remove the solvent in the coating film 300 .
  • Step Sb In step Sb, by irradiating the coating film 300 with the active energy ray E through the photomask 301, the coating film 300 is formed into an exposed portion 300a composed of a semi-cured photosensitive composition and a non-exposed portion 300b. form (FIG. 6B). An opening 301a is formed in the photomask 301 at a position corresponding to the exposure portion 300a. As a result, only the coating film 300 (exposed portion 300a) positioned below the opening 301a is exposed, and the photocuring reaction proceeds.
  • the integrated exposure amount during exposure is not particularly limited, but is preferably 1 mJ/cm 2 or more and 10000 mJ/cm 2 or less, more preferably 1 mJ/cm 2 or more and 4000 mJ/cm 2 or less.
  • the wavelength of the active energy ray E irradiated in step Sb is, for example, in the range of 200 nm or more and 450 nm or less.
  • Light sources for active energy rays E include high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, high power metal halide lamps, xenon lamps, carbon arc lamps and light emitting diodes.
  • the irradiation time of the active energy ray E is preferably 1 second or more and 600 seconds or less, more preferably 1 second or more and 150 seconds or less.
  • a patterned coating film is formed on the first substrate 11 by removing (developing) the non-exposed portions 300b from the first substrate 11 with an alkaline developer.
  • the alkaline developer used in step Sc is, for example, an aqueous solution containing an alkaline component.
  • Alkaline components include alkaline organic components and alkaline inorganic components. Examples of alkaline organic components include tetramethylammonium hydroxide (TMAH) and choline. Examples of alkaline inorganic components include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, and lithium carbonate.
  • the concentration of the alkaline component in the alkaline developer is preferably 25% by mass or less, more preferably 10% by mass or less, and 5% by mass. % or less.
  • the method of removing the non-exposed portion 300b from the first substrate 11 with the alkaline developer is not particularly limited. Methods of dissolving and removing portion 300b are included.
  • the coating film 300 may be washed with water after the coating film 300 is brought into contact with the alkaline developer.
  • the coating film 300 is washed with water, it is preferable to remove moisture on the surface of the coating film 300 with compressed air after washing with water.
  • step Sd the pattern film formed in step Sc (a film composed of the semi-cured photosensitive composition) is heated to further cure the semi-cured photosensitive composition, thereby forming a pattern.
  • a first layer 131 composed of the cured product is obtained (FIG. 6C).
  • the temperature for heating the pattern film in step Sd is preferably 80° C. or higher and 350° C. or lower, and more preferably 150° C. or higher and 250° C. or lower.
  • the substrate laminate obtained by the manufacturing method according to the first embodiment is excellent in reliability evaluated by a thermal shock test.
  • step Se is performed, and the content of the alkali component in the first layer 131 before step Se (before step Se) is preferably 1000 ppm or less, and preferably 200 ppm or less. is more preferable, and 150 ppm or less is even more preferable.
  • the lower limit of the alkaline component content in the first layer 131 before step Se is not particularly limited, but is, for example, 1 ppm or more.
  • the substrate laminate constitutes an image sensor
  • the function as the image sensor may deteriorate.
  • the high-temperature and high-humidity storage stability (the ability to suppress the increase of foreign substances in the hollow portion Z even when stored under high-temperature and high-humidity conditions) deteriorates.
  • At least part of the alkali component in the first layer 131 can be removed when the pattern film is heated in step Sd. It can be adjusted by changing Also, the content of the alkali component in the first layer 131 before step Se can be adjusted by changing the composition of the photosensitive composition used.
  • the method for measuring the content of the alkali component in the first layer 131 before step Se is the same method as in Examples described later or a method based thereon.
  • the softening point of the first layer 131 before step Se is preferably 100° C. or higher, more preferably 150° C. or higher.
  • the upper limit of the softening point of the first layer 131 before step Se is not particularly limited, but is, for example, 250° C. or less.
  • the softening point of the first layer 131 before step Se can be adjusted, for example, by changing the heating conditions in step Sd.
  • the method for measuring the softening point of the first layer 131 before the step Se is the same method as in Examples described later or a method based thereon.
  • the elastic modulus of the first layer 131 before step Se measured by the nanoindentation test method at a temperature of 100° C. (hereinafter sometimes simply referred to as “elastic modulus of the first layer 131”) is 1500 N/ mm 2 or more is preferable, and 2000 N/mm 2 or more is more preferable.
  • the upper limit of the elastic modulus of the first layer 131 is not particularly limited, it is, for example, 5000 N/mm 2 or less.
  • the elastic modulus of the first layer 131 can be adjusted, for example, by changing the heating conditions in step Sd.
  • the method for measuring the elastic modulus of the first layer 131 is the same method as in Examples described later or a method based thereon.
  • step Se after bonding the first layer 131 and the second substrate 12 together via an adhesive 400 (see FIG. 7A), the adhesive 400 is cured to bond the first layer 131 and the second substrate 12 together.
  • An adhering second layer 132 (see FIG. 7C) is obtained.
  • the adhesive 400 is applied onto the first layer 131 with a syringe or the like.
  • FIG. 7A shows an example in which the adhesive 400 is applied to the surface (end surface) of the first layer 131 opposite to the first substrate 11 side, but the present invention is not limited to this, and the second substrate 12 may be coated with the adhesive 400 , or both the first layer 131 and the second substrate 12 may be coated with the adhesive 400 .
  • the adhesive 400 may be applied to at least a portion of the wall surface and end surfaces of the first layer 131 .
  • the method of applying the adhesive 400 is not limited to the method of applying with a syringe.
  • the adhesive 400 may be applied by a screen printing method, a stamp method, or the like.
  • the first layer 131 and the large-sized second substrate 12 are bonded together via an adhesive 400 (FIG. 7B).
  • the adhesive 400 is cured to obtain the second layer 132 (see FIG. 7C) that bonds the first layer 131 and the second substrate 12 together.
  • a method for curing the adhesive 400 may be appropriately selected according to the type of the adhesive 400 . Specific examples of the method for curing the adhesive 400 include a curing method by heating and a curing method by ultraviolet irradiation.
  • Step Sf2 After the step Se, the laminate obtained by laminating the large-sized first substrate 11, the first layer 131, the second layer 132, and the large-sized second substrate 12 in this order is diced to separate into pieces. It is a step of obtaining a laminated product. For example, after curing the adhesive 400 in the laminate shown in FIG. 7B in step Se, by dicing along the dividing lines 401 in FIG. 7B, the substrate laminate 10 ( FIG. 7C) can be obtained.
  • step Sf2 is performed in the method shown in FIGS. 7A to 7C
  • the manufacturing method according to the first embodiment is not limited to this.
  • the laminate of the large-sized first substrate 11 and the first layer 131 is separated along the parting line 200 in FIG.
  • a step Sf1 of obtaining an individualized laminate shown in FIG. 8 (hereinafter sometimes referred to as “individualized laminate”) by dicing may be further included.
  • the singulated laminate shown in FIG. 8 includes the singulated first substrate 11 and one first layer 131 .
  • process Sf2 is not implemented.
  • the manufacturing method of the substrate laminate according to the first embodiment further includes the step Sf1 in the step Se, the first layer 131 of the singulated laminate and the second substrate 12 are attached via the adhesive 400. to paste together.
  • the manufacturing method according to the first embodiment further includes the step Sf1
  • the first layer 131 of the plurality of singulated laminates and the large-sized second substrate 12 are attached via the adhesive 400.
  • the adhesive 400 may be cured after the bonding.
  • a plurality of substrate laminates can be obtained by cutting the large-sized second substrate 12 for each first layer 131 after curing the adhesive 400 .
  • first substrate and second substrate examples include silicon wafers, glass substrates, resin substrates (such as transparent resin substrates), ceramic substrates, and semiconductor element substrates.
  • semiconductor element substrates include sensor substrates (more specifically, image sensor substrates, etc.).
  • the first substrate and the second substrate may be substrates of the same kind or substrates of different kinds.
  • the substrate laminate can be applied as a constituent member of an optical component.
  • a substrate laminate in which one of the first substrate and the second substrate is a transparent substrate and the other is a semiconductor element substrate is suitable for an image sensor.
  • the thickness of the first substrate and the thickness of the second substrate are, for example, 50 ⁇ m or more and 2000 ⁇ m or less, respectively.
  • the thickness of the semiconductor element substrate is, for example, 50 ⁇ m or more and 800 ⁇ m or less.
  • the thickness of the first substrate and the thickness of the second substrate may be the same or different.
  • a 1st layer is comprised from the hardened
  • the details of the photosensitive composition that is the material of the first layer will be described later.
  • the height (thickness) of the first layer is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, and 300 ⁇ m or less in order to obtain a substrate laminate with excellent reliability evaluated by a thermal shock test. is more preferably 150 ⁇ m or less, and may be 140 ⁇ m or less, 130 ⁇ m or less, 120 ⁇ m or less, 110 ⁇ m or less, or 100 ⁇ m or less.
  • the height of the first layer is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, in order to suppress the reflection of foreign matter adhering to the transparent substrate. More preferably 20 ⁇ m or more, even more preferably 30 ⁇ m or more, and may be 40 ⁇ m or more.
  • the width of the first layer is, for example, 10 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 200 ⁇ m or less, and more preferably 20 ⁇ m or more and 150 ⁇ m or less.
  • the second layer is composed of a cured adhesive.
  • the adhesive used as the material for the second layer include thermosetting adhesives (more specifically, epoxy-based adhesives, etc.), ultraviolet-curable adhesives (more specifically, acrylic-based adhesives, etc.), and the like. be done.
  • the term “acrylic adhesive” refers to (meth)acrylic acid or derivatives thereof (more specifically, (meth)acrylic acid esters, etc.), or polymers of (meth)acrylic acid or derivatives thereof as main components. means an adhesive that
  • an epoxy-based adhesive is preferable as the adhesive used as the material for the second layer.
  • the main agent of the epoxy-based adhesive must contain two or more epoxy groups. Aromatic epoxy compounds having preferable.
  • an imidazole-based curing agent is used as the curing agent for the epoxy-based adhesive in order to obtain a substrate laminate with superior adhesion between substrates. preferable.
  • the adhesive used as the material for the second layer should be an epoxy containing a bisphenol-based diglycidyl ether as a main component and an imidazole-based curing agent as a curing agent.
  • An epoxy-based adhesive containing bisphenol A diglycidyl ether as a main component and an imidazole-based curing agent as a curing agent is more preferable.
  • the mass ratio of the main agent and the curing agent (main agent/curing agent) in the epoxy adhesive is, for example, 100/1 or more and 100/10 or less.
  • the height (thickness) of the second layer should be 0.01 ⁇ m or more and 100 ⁇ m or less in order to obtain a substrate laminate that is excellent in reliability evaluated by a thermal shock test while having excellent adhesion between substrates. It is preferably 0.1 ⁇ m or more and 80 ⁇ m or less, still more preferably 0.5 ⁇ m or more and 50 ⁇ m or less, and even more preferably 1 ⁇ m or more and 20 ⁇ m or less.
  • the width of the second layer can be appropriately changed according to the width of the first layer, and is, for example, 10 ⁇ m or more and 500 ⁇ m or less, preferably 10 ⁇ m or more and 200 ⁇ m or less, more preferably 20 ⁇ m or more and 150 ⁇ m or less.
  • the width of the second layer when the width of the first layer is 100% is preferably 70% or more, preferably 80%. It is more preferably 90% or more, more preferably 90% or more, and may be 100% or more, 110% or more, or 120% or more.
  • the photosensitive composition that is the material of the first layer contains a curable compound having a cationic polymerizable group and a photocationic polymerization initiator, and has alkali solubility.
  • the cationic polymerizable groups include epoxy groups, vinyl ether groups, oxetanyl groups, and alkoxysilyl groups.
  • the cationically polymerizable group is preferably one or more selected from the group consisting of a glycidyl group, an alicyclic epoxy group and an oxetanyl group. More preferably, one or more selected from the group consisting of epoxy groups.
  • an alicyclic epoxy group is particularly preferable because of its excellent cationic photopolymerizability.
  • the first substrate is a glass substrate.
  • the photosensitive composition used as the material for the first layer is selected from the group consisting of the glycidyl group and the alicyclic epoxy group.
  • the photosensitive composition that is the material of the first layer contains a curable compound having one or more selected from the group consisting of glycidyl groups and alicyclic epoxy groups, the first layer and the second layer
  • a curable compound having one or more selected from the group consisting of glycidyl groups and alicyclic epoxy groups the first layer and the second layer
  • an epoxy-based adhesive it is preferable to use an epoxy-based adhesive as the adhesive that is the material of the second layer.
  • curable compound having a cationic polymerizable group examples include polysiloxane compounds having a cationic polymerizable group, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac phenol type epoxy resin, biphenyl type epoxy resin, dicyclo pentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis(4-glycidyloxycyclohexyl)propane, vinylcyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5, 5-spiro-(3,4-epoxycyclohexane)-1,3-dioxane, bis(3,4-epoxycyclohexyl)adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl di Glycidyl isocyanurate, dial
  • the photosensitive composition that is the material of the first layer has alkali solubility by containing a compound having an alkali-soluble group.
  • the compound having an alkali-soluble group include polysiloxane compounds having an alkali-soluble group, resins having a phenolic hydroxyl group (e.g., novolac resins having a phenolic hydroxyl group), resins having a carboxyl group (e.g., ( copolymers of meth)acrylic acid and (meth)acrylic acid ester), and the like.
  • the photosensitive composition used as the material for the first layer must have a curable composition having the above cationic polymerizable group.
  • a curable composition having the above cationic polymerizable group it is preferable to contain a polysiloxane compound having a cationic polymerizable group.
  • the photosensitive composition which is the material for the first layer, must be a curable compound having the above cationic polymerizable group and the above alkali-soluble As the compound having a group, it is preferable to contain a polysiloxane compound having a cationic polymerizable group and an alkali-soluble group in one molecule.
  • the photosensitive composition which is the material for the first layer, contains a cationic polymerizable group and an alkali-soluble group in one molecule.
  • component (A) a polysiloxane compound
  • component (B) a photocationic polymerization initiator
  • the photosensitive composition containing component (A) and component (B) may be referred to as “specific photosensitive composition”.
  • specific photosensitive composition The components contained in the specific photosensitive composition are described in detail below.
  • Component (A) is not particularly limited as long as it is a polysiloxane compound having a cationic polymerizable group and an alkali-soluble group in one molecule.
  • Component (A) has a cationic polymerizable group and an alkali-soluble group in one molecule, it is possible to obtain a specific photosensitive composition which is excellent in both developability and curability.
  • Component (A) preferably has a plurality of cationic polymerizable groups in one molecule.
  • the component (A) has a plurality of cationic polymerizable groups in one molecule, the first layer with a high crosslink density is obtained, and as a result, the heat resistance of the first layer tends to be further improved.
  • the plurality of cationically polymerizable groups may be of the same type or may be two or more different functional groups.
  • component (A) preferably has a plurality of alkali-soluble groups in one molecule.
  • the plurality of alkali-soluble groups may be of the same kind or may be two or more different functional groups.
  • Component (A) may have a chain polysiloxane structure or a cyclic polysiloxane structure.
  • Component (A) preferably has a cyclic polysiloxane structure in order to form a first layer with superior heat resistance.
  • the specific photosensitive composition tends to have high film-forming properties and developability.
  • the component (A) may have a polysiloxane structure in its main chain and may have a polysiloxane structure in its side chains.
  • component (A) preferably has a polysiloxane structure in its main chain.
  • component (A) preferably has a cyclic polysiloxane structure in its main chain.
  • the cyclic polysiloxane structure may be a monocyclic structure or a polycyclic structure.
  • the polycyclic structure may be a polyhedral structure.
  • T units XSiO 3/2
  • Q units SiO 4/2
  • M units X 3 SiO 1/2
  • D units X 2 SiO 2/2
  • the weight average molecular weight of the polymer is preferably 10,000 or more and 50,000 or less, more preferably 20,000 or more and 40,000 or less.
  • the weight-average molecular weight is 10,000 or more, the heat resistance of the obtained first layer tends to be further improved.
  • the weight average molecular weight is 50,000 or less, the developability tends to be further improved.
  • Examples of cationically polymerizable groups possessed by component (A) include epoxy groups, vinyl ether groups, oxetanyl groups, and alkoxysilyl groups.
  • the cationically polymerizable group is preferably one or more selected from the group consisting of a glycidyl group, an alicyclic epoxy group and an oxetanyl group. More preferably, one or more selected from the group consisting of epoxy groups.
  • an alicyclic epoxy group is particularly preferable because of its excellent cationic photopolymerizability.
  • Examples of the alkali-soluble group that the component (A) has include a monovalent organic group represented by the following chemical formula (X1) (hereinafter sometimes referred to as "X1 group”) and a chemical formula (X2) below. At least one selected from the group consisting of a divalent organic group (hereinafter sometimes referred to as "X2 group”), a phenolic hydroxyl group, and a carboxy group is preferred.
  • the X1 group is a monovalent organic group derived from N-monosubstituted isocyanuric acid.
  • the X2 group is a divalent organic group derived from N,N'-disubstituted isocyanuric acid.
  • the alkali-soluble group of component (A) is preferably one or more selected from the group consisting of X1 group and X2 group.
  • component (A) is preferably a polysiloxane compound that has been organically modified by a hydrosilylation reaction and into which cationic polymerizable groups have been introduced via silicon-carbon bonds.
  • the alkali-soluble group is also preferably introduced into the polysiloxane compound through a silicon-carbon bond by a hydrosilylation reaction.
  • Component (A) can be obtained, for example, by a hydrosilylation reaction using the following compound ( ⁇ ), compound ( ⁇ ) and compound ( ⁇ ) as starting materials.
  • ⁇ Compound ( ⁇ ) A polysiloxane compound having at least two SiH groups (hydrosilyl groups) in one molecule
  • ⁇ Compound ( ⁇ ) A carbon-carbon double bond having reactivity with SiH groups in one molecule and a cationic polymerizable group/compound ( ⁇ ): a compound having a carbon-carbon double bond reactive with an SiH group and an alkali-soluble group in one molecule
  • Compound ( ⁇ ) is a polysiloxane compound having at least two SiH groups in one molecule, for example, the compound described in WO 96/15194, which has at least two SiH groups in one molecule. You can use what you have.
  • Specific examples of the compound ( ⁇ ) include a hydrosilyl group-containing polysiloxane having a linear structure, a polysiloxane having a hydrosilyl group at the molecular end, and a cyclic polysiloxane having a hydrosilyl group (hereinafter simply referred to as “cyclic polysiloxane”). sometimes), etc.
  • the cyclic polysiloxane may have a polycyclic structure, and the polycyclic structure may be a polyhedral structure.
  • a cyclic polysiloxane having at least two SiH groups in one molecule as the compound ( ⁇ ).
  • Compound ( ⁇ ) is preferably a cyclic polysiloxane having 3 or more SiH groups in one molecule.
  • the group present on the Si atom is preferably either a hydrogen atom or a methyl group.
  • hydrosilyl group-containing polysiloxanes having a linear structure examples include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, and copolymers of diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units.
  • examples include polymers, copolymers of methylphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, and polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups.
  • polysiloxanes having hydrosilyl groups at their molecular terminals include polysiloxanes whose terminals are blocked with dimethylhydrogensilyl groups, dimethylhydrogensiloxane units (H(CH 3 ) 2 SiO 1/2 units), and SiO 2 units. , SiO 3/2 units and one or more siloxane units selected from the group consisting of SiO units.
  • the cyclic polysiloxane is represented, for example, by the following general formula (I).
  • R 1 , R 2 and R 3 each independently represent a monovalent organic group having 1 to 20 carbon atoms
  • m represents an integer of 2 to 10
  • n is It represents an integer of 0 or more and 10 or less.
  • m is preferably 3 or more.
  • m+n is preferably 3 or more and 12 or less.
  • n is 0 in order to facilitate the hydrosilylation reaction.
  • R 1 , R 2 and R 3 are preferably organic groups composed of elements selected from the group consisting of C, H and O.
  • R 1 , R 2 and R 3 include alkyl groups, hydroxyalkyl groups, alkoxyalkyl groups, oxyalkyl groups, aryl groups and the like. Among them, chain alkyl groups such as methyl group, ethyl group, propyl group, hexyl group, octyl group, decyl group and dodecyl group; cyclic alkyl groups such as cyclohexyl group and norbornyl group; and phenyl group are preferred.
  • R 1 , R 2 and R 3 are preferably chain alkyl groups having 1 to 6 carbon atoms or phenyl groups.
  • each of R 1 , R 2 and R 3 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group. .
  • Cyclic polysiloxanes represented by general formula (I) include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7 -trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3 ,5-trihydrogen-1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, and 1 , 3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane and the like. Among them, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (
  • the compound ( ⁇ ) is obtained by a known synthetic method.
  • the cyclic polysiloxane represented by general formula (I) can be synthesized by the method described in International Publication No. 96/15194.
  • a cyclic polysiloxane having a polyhedral skeleton can be synthesized, for example, by the methods described in JP-A-2004-359933, JP-A-2004-143449, JP-A-2006-269402, and the like.
  • the content of the structural unit derived from the compound ( ⁇ ) in the component (A) is 100 mass of the component (A). %, preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 45% by mass or less.
  • the compound ( ⁇ ) is a compound having, in one molecule, a carbon-carbon double bond reactive with an SiH group (hydrosilyl group) and a cationically polymerizable group, and a cationically polymerizable group in the polysiloxane compound. is a compound for introducing The cationically polymerizable group in the compound ( ⁇ ) is the same as the cationically polymerizable group of the component (A) described above, and preferred embodiments are also the same.
  • the compound ( ⁇ ) preferably has one or more selected from the group consisting of a glycidyl group, an alicyclic epoxy group and an oxetanyl group as a cationically polymerizable group. It is more preferable to have one or more selected from the group consisting of, more preferably to have an alicyclic epoxy group.
  • alkenyl groups include, for example, vinyl groups, allyl groups, methallyl groups, allyloxy groups (- O—CH 2 —CH ⁇ CH 2 ), 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2-(allyloxy)phenyl group, 3-(allyloxy)phenyl group, 4-(allyloxy) phenyl group, 2-(allyloxy)ethyl group, 2,2-bis(allyloxymethyl)butyl group, 3-allyloxy-2,2-bis(allyloxymethyl)propyl group, vinyl ether group and the like.
  • the compound ( ⁇ ) preferably has one or more alkenyl groups selected from the group consisting of vinyl groups, allyl groups and allyloxy groups. It is more preferable to have one or more selected from the group consisting of:
  • the compound ( ⁇ ) examples include 1-vinyl-3,4-epoxycyclohexane, allyl glycidyl ether, allyl oxetanyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and the like.
  • the compound ( ⁇ ) is preferably a compound having one or more functional groups selected from the group consisting of an alicyclic epoxy group and a glycidyl group, and has an alicyclic epoxy group. Compounds are more preferred.
  • the compound ( ⁇ ) is preferably one or more compounds selected from the group consisting of allyl glycidyl ether and 1-vinyl-3,4-epoxycyclohexane. Vinyl-3,4-epoxycyclohexane is more preferred.
  • the content of the structural unit derived from the compound ( ⁇ ) in the component (A) is 100 mass of the component (A). %, preferably 20% by mass or more and 50% by mass or less, more preferably 22% by mass or more and 45% by mass or less.
  • Compound ( ⁇ ) is a compound having a carbon-carbon double bond reactive with SiH groups and an alkali-soluble group in one molecule, and is a compound for introducing an alkali-soluble group into a polysiloxane compound. is.
  • the alkali-soluble group in compound ( ⁇ ) is the same as the alkali-soluble group of component (A) described above, and preferred embodiments are also the same. That is, the compound ( ⁇ ) preferably has, as an alkali-soluble group, one or more selected from the group consisting of X1 group, X2 group, phenolic hydroxyl group and carboxy group, and from the group consisting of X1 group and X2 group, It is more preferable to have one or more selected.
  • the compound ( ⁇ ) has a group (alkenyl group) containing a carbon-carbon double bond that is reactive with SiH groups.
  • alkenyl group possessed by the compound ( ⁇ ) include the same alkenyl groups as those exemplified as the alkenyl group possessed by the compound ( ⁇ ) described above, and preferred embodiments are also the same. That is, the compound ( ⁇ ) preferably has, as an alkenyl group, one or more selected from the group consisting of a vinyl group, an allyl group and an allyloxy group, and one selected from the group consisting of a vinyl group and an allyl group. It is more preferable to have
  • the compound ( ⁇ ) may have two or more alkenyl groups in one molecule.
  • compound ( ⁇ ) contains a plurality of alkenyl groups in one molecule, a plurality of compounds ( ⁇ ) can be crosslinked by hydrosilylation reaction, so that the crosslink density of the resulting cured product increases and the heat resistance of the cured product increases. tend to improve.
  • the compound ( ⁇ ) include diallyl isocyanurate, monoallyl isocyanurate, 2,2′-diallyl bisphenol A, vinylphenol, allylphenol, butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, undecylenic acid, and the like. is mentioned.
  • the compound ( ⁇ ) is one or more selected from the group consisting of diallyl isocyanurate, monoallyl isocyanurate and 2,2′-diallyl bisphenol A. More preferably, one or more selected from the group consisting of diallyl isocyanurate and monoallyl isocyanurate.
  • component (A) having X1 group as alkali-soluble group is obtained.
  • diallyl isocyanurate is used as the compound ( ⁇ )
  • the component (A) having X2 group as an alkali-soluble group is obtained.
  • the content of the structural unit derived from the compound ( ⁇ ) in the component (A) is 5% by mass or more and 50% by mass with respect to 100% by mass of the component (A). % or less, more preferably 10% by mass or more and 30% by mass or less.
  • an alkenyl group-containing compound (hereinafter sometimes referred to as "another alkenyl group-containing compound") different from the above compounds ( ⁇ ) and ( ⁇ ) may be used.
  • compound ( ⁇ ) a compound having two or more alkenyl groups in one molecule
  • compound ( ⁇ ) a compound having two or more alkenyl groups in one molecule
  • compound ( ⁇ ) is used as another alkenyl group-containing compound.
  • the number of cross-linking points increases during the hydrosilylation reaction, so that the heat resistance of the first layer obtained tends to be further improved.
  • the compound ( ⁇ ) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, 1,1,2,2-tetraallyloxyethane, triallyl cyanurate, triallyl isocyanurate, and diallyl monobenzyl.
  • the compound ( ⁇ ) is preferably one or more selected from the group consisting of triallyl isocyanurate and diallyl monomethyl isocyanurate, and diallyl monomethyl isocyanurate is preferred. more preferred.
  • the content of the structural unit derived from the compound ( ⁇ ) in the component (A) should be 100% by mass of the component (A). , preferably 5% by mass or more and 30% by mass or less, more preferably 8% by mass or more and 20% by mass or less.
  • component (A) The order and method of the hydrosilylation reaction to obtain component (A) are not particularly limited.
  • Component (A) is obtained by the hydrosilylation reaction.
  • the component (A) obtained using the above-described compound ( ⁇ ), compound ( ⁇ ), compound ( ⁇ ), and optionally other optional starting materials is, for example, a plurality of It is a polymer having a cationic polymerizable group and a plurality of alkali-soluble groups and having a polysiloxane structure in its main chain.
  • the ratio of each compound in the hydrosilylation reaction is not particularly limited, but the total amount A of alkenyl groups and the total amount B of SiH groups in the starting materials preferably satisfy 1 ⁇ B/A ⁇ 30, and 1 ⁇ It is more preferable to satisfy B/A ⁇ 10.
  • Hydrosilylation catalysts such as chloroplatinic acid, platinum-olefin complexes and platinum-vinylsiloxane complexes may be used in the hydrosilylation reaction.
  • a hydrosilylation catalyst and co-catalyst may be used in combination.
  • the amount (amount of substance) added of the hydrosilylation catalyst is not particularly limited, but is preferably 10 ⁇ 8 times or more and 10 ⁇ 1 times or less, more preferably 10 ⁇ 6 times the total amount of alkenyl groups contained in the starting material. It is more than 10 -2 times or less.
  • the reaction temperature for hydrosilylation may be appropriately set, preferably 30°C or higher and 200°C or lower, more preferably 50°C or higher and 150°C or lower.
  • the oxygen concentration in the gas phase in the hydrosilylation reaction is preferably 3% by volume or less. From the viewpoint of promoting the hydrosilylation reaction, the gas phase portion may contain 0.1% by volume or more and 3% by volume or less of oxygen.
  • a solvent may be used for the hydrosilylation reaction.
  • a single solvent or a mixed solvent in which two or more kinds are mixed can be used.
  • Solvents include hydrocarbon solvents such as benzene, toluene, xylene, hexane and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone. ; Halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be used.
  • Toluene, xylene, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, or chloroform are preferred because they are easily distilled off after the reaction.
  • a gelation inhibitor may be used in the hydrosilylation reaction, if desired.
  • the content of component (A) in the specific photosensitive composition is 20% by mass or more and 95% by mass with respect to the total solid content of the specific photosensitive composition. % or less.
  • Component (B) for example, a known cationic photopolymerization initiator can be used.
  • the component (B) include, but are not limited to, various compounds that are considered suitable in JP-A-2000-1648, JP-A-2001-515533, WO 2002/83764, and the like.
  • Component (B) is preferably a sulfonate ester compound, a carboxylic acid ester compound or an onium salt compound, more preferably an onium salt compound, and still more preferably a sulfonium salt compound.
  • sulfonate ester compound various sulfonic acid derivatives can be used. compounds, pyrogalloltrisulfonate-based compounds and benzylsulfonate-based compounds.
  • sulfonate ester compounds include diphenyldisulfone, ditosyldisulfone, bis(phenylsulfonyl)diazomethane, bis(chlorophenylsulfonyl)diazomethane, bis(xylylsulfonyl)diazomethane, phenylsulfonylbenzoyldiazomethane, and bis(cyclohexylsulfonyl).
  • a carboxylic acid ester compound can also be used as component (B).
  • Onium salt compounds include sulfonium salt compounds and iodonium salt compounds.
  • Examples of anions possessed by sulfonium salt compounds and iodonium salt compounds include tetrafluoroborate (BF 4 ⁇ ), hexafluorophosphate (PF 6 ⁇ ), hexafluoroantimonate (SbF 6 ⁇ ), hexafluoroarsenate (AsF 6 ⁇ ), hexachloroantimonate (SbCl 6 ⁇ ), tetraphenylborate, tetrakis(trifluoromethylphenyl)borate, tetrakis(pentafluoromethylphenyl)borate, fluoroalkylfluorophosphate, perchlorate ion (ClO 4 ⁇ ) , trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), fluorosulfonate ion (FSO 3
  • the photocationic polymerization initiators are arranged in descending order of acid strength of the generated acid . as an anion, a compound containing CF 3 SO 3 - as an anion, and a compound containing HSO 4 - as an anion.
  • the use of a photocationic polymerization initiator that generates an acid with a high acid strength tends to increase the residual film rate.
  • the pKa of the acid generated from the photocationic polymerization initiator is preferably less than 3, more preferably less than 1.
  • the cations possessed by the sulfonium salt compounds include cations represented by the following chemical formula (II) and cations represented by the following general formula (III).
  • R 4 , R 5 and R 6 in general formula (III) below each independently represent an alkyl group.
  • sulfonium salt photocationic polymerization initiators include, for example, fluoroalkylfluorophosphate (anion) and a photocationic polymerization initiator containing a cation represented by the chemical formula (II). (“CPI-210S” manufactured by San-Apro Co., Ltd.).
  • Examples of cations possessed by iodonium salt compounds include cations represented by the following general formula (IV).
  • R 7 and R 8 in the following general formula (IV) each independently represent an alkyl group.
  • the content of component (B) in the specific photosensitive composition is not particularly limited. From the viewpoint of the curing speed and physical property balance of the cured product, the content of component (B) is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of component (A). It is more preferably 5 parts by mass or more and 10 parts by mass or less.
  • the specific photosensitive composition may contain a solvent.
  • the specific photosensitive composition can be obtained by dissolving or dispersing the components (A) and (B) described above, and optionally other components described below, in a solvent.
  • solvents include hydrocarbon solvents such as benzene, toluene, hexane and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and diethyl ether; acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • ketone solvents such as cyclohexanone
  • glycol solvents such as propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethylene glycol diethyl ether
  • ester solvents such as isobutyl isobutyrate
  • chloroform methylene chloride
  • examples include halogen-based solvents such as 1,2-dichloroethane.
  • the solvent is preferably a glycol-based solvent, more preferably propylene glycol 1-monomethyl ether 2-acetate.
  • the amount of the solvent is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the component (A). More preferably, the amount is not less than 80 parts by mass.
  • the specific photosensitive composition contains components (other components) other than the above components (A) and (B) as solids (components other than the solvent) within a range that does not impair the object and effect of the present invention. You may however, in order to obtain a substrate laminate having excellent adhesion between substrates while forming a first layer having excellent heat resistance, the total content of component (A) and component (B) must be within the specific photosensitive composition. It is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and 80% by mass or more and 100% by mass or less. is even more preferred.
  • Other components include reactive diluents, cross-linking agents, basic compounds, sensitizers, adhesion improvers, thermoplastic resins, fillers, antioxidants, radical inhibitors, polymer dispersants, mold release agents. , flame retardant, flame retardant aid, surfactant, antifoaming agent, emulsifier, leveling agent, anti-repellent agent, ion trapping agent (antimony-bismuth, etc.), thixotropic agent, tackifier, storage stability improver , antiozonants, light stabilizers, thickeners, plasticizers, heat stabilizers, conductivity imparting agents, antistatic agents, radiation shielding agents, nucleating agents, phosphorus peroxide decomposers, lubricants, metal Examples include activators, thermal conductivity imparting agents, and physical property modifiers.
  • the specific photosensitive composition may contain a reactive diluent.
  • a reactive diluent is a component that participates in the curing reaction while reducing the viscosity of the specific photosensitive composition.
  • the reactive diluent for example, a compound having two or more cationic polymerizable groups in one molecule is used.
  • the cationic polymerizable group of the reactive diluent include those exemplified as the cationic polymerizable group possessed by the component (A) described above.
  • the cationically polymerizable group of the reactive diluent may be of the same type as the cationically polymerizable group of component (A), or may be of a different type.
  • the reactive diluent preferably has an alicyclic epoxy group as a cationic polymerizable group.
  • component (A) contains an alicyclic epoxy group as the cationically polymerizable group, and the reactive diluent has two or more alicyclic epoxy groups per molecule.
  • Compounds having two or more alicyclic epoxy groups in one molecule include 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate ("Celoxide (registered trademark) 2021P” manufactured by Daicel Corporation), ⁇ -caprolactone-modified 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate ("Celoxide (registered trademark) 2081" manufactured by Daicel), bis(3,4-epoxycyclohexylmethyl) adipate and the like. .
  • 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (“Celoxide (registered trademark) 2021P” manufactured by Daicel Corporation)
  • the content of the reactive diluent is 2% by mass or more and 50% by mass with respect to the total solid content of the specific photosensitive composition, from the viewpoint of achieving both an improvement in the curing speed of the specific photosensitive composition and a balance of physical properties of the cured product. % or less, more preferably 3% by mass or more and 40% by mass or less.
  • the specific photosensitive composition may contain a cross-linking agent from the viewpoint of workability, reactivity, adhesiveness, and adjustment of the strength of the first layer.
  • a cross-linking agent is a compound having two or more photopolymerizable functional groups other than a cationic polymerizable group in one molecule. Examples of cross-linking agents include alkoxysilane compounds and (meth)acrylate compounds.
  • the specific photosensitive composition may contain a basic compound.
  • Basic compounds act as quenchers. That is, by adding an appropriate amount of basic compound to the specific photosensitive composition, it is possible to prevent the photocuring reaction from extending to the non-exposed areas. This makes the contrast between the exposed and non-exposed areas clear, resulting in improved resolution.
  • the amount of the basic compound is preferably 0.001 parts by mass or more and 2.0 parts by mass or less, more preferably 0.01 parts by mass or more and 1.0 parts by mass, per 100 parts by mass of component (A). It is below. If the blending amount of the basic compound is 0.001 parts by mass or more, the function as a quencher can be sufficiently exhibited. If the blending amount of the basic compound is 2.0 parts by mass or less, the sensitivity can be improved.
  • the mass ratio of the basic compound to the photocationic polymerization initiator is, for example, 0.001 or more and 0.2 or less, preferably 0.01 or more and 0.15 or less. If the mass ratio is 0.001 or more, the function as a quencher can be sufficiently exhibited. If the said mass ratio is 0.2 or less, it can fully bridge
  • Basic compounds include, but are not limited to, primary, secondary and tertiary aliphatic amine compounds, mixed amine compounds, aromatic amine compounds, heterocyclic amine compounds, amide derivatives, imides derivatives and the like.
  • aromatic amine-based compounds and heterocyclic amine-based compounds can be suitably used as basic compounds.
  • aromatic amine-based compound and the heterocyclic amine-based compound examples include aniline, pyrrole, oxazole, thiazole, imidazole, pyrazole, furazane, pyrroline, pyrrolidine, imidazoline, imidazolidine, pyridine, pyridazine, pyrimidine, pyrazine, pyrazoline, and pyrazolidine.
  • one type may be used, or two or more types may be used in combination.
  • the specific photosensitive composition may contain a sensitizer.
  • a sensitizer improves the exposure sensitivity during patterning.
  • an anthracene-based compound is preferred.
  • anthracene compounds include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-di Ethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-t-butylanthracene, 2,6-di-t-butylanthracene, 9,10-diphenyl-2,6-di- and t-butylanthracene.
  • 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene 9,10-dibutoxyanthracene
  • the content of the sensitizer in the specific photosensitive composition is not particularly limited, but from the viewpoint of curability and physical property balance of the cured product, 0.01 parts by mass or more with respect to 100 parts by mass of component (A) It is preferably 20 parts by mass or less, and more preferably 0.1 parts by mass or more and 15 parts by mass or less.
  • Adhesion improver The specific photosensitive composition may contain an adhesion improver.
  • Adhesion improvers include, for example, various coupling agents, epoxy compounds, oxetane compounds, phenolic resins, coumarone-indene resins, rosin ester resins, terpene-phenolic resins, ⁇ -methylstyrene-vinyltoluene copolymers, poly Ethylmethylstyrene and aromatic polyisocyanates can be mentioned.
  • Examples of coupling agents include silane coupling agents.
  • the silane coupling agent is not particularly limited as long as it is a compound having at least one reactive functional group and at least one hydrolyzable silicon-containing group in the molecule.
  • the reactive functional group is preferably one or more functional groups selected from the group consisting of an epoxy group, a (meth)acrylic group, an isocyanate group, an isocyanurate group, a vinyl group and a carbamate group, from the viewpoint of handling properties, and cured.
  • Epoxy group, methacrylic group or acrylic group is particularly preferable from the viewpoint of properties and adhesiveness.
  • As the hydrolyzable silicon-containing group an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group or an ethoxysilyl group is particularly preferable from the viewpoint of reactivity.
  • Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4- Alkoxysilane compounds having an epoxy group such as epoxycyclohexyl)ethyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Alkoxysilane compounds having (meth)acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane; tris[3-( trimethoxysilylpropyl)]isocyanur
  • the amount of the silane coupling agent added can be appropriately set, but is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.3 parts by mass, relative to 100 parts by mass of the compound having a cationically polymerizable group. parts or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less.
  • the specific photosensitive composition may contain a thermoplastic resin.
  • thermoplastic resins include acrylic resins, polycarbonate resins, cycloolefin resins, olefin-maleimide resins, polyester resins, polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, polyethylene resins, polypropylene resins, Polystyrene resins, polyamide resins, silicone resins, fluororesins, rubber-like resins and the like can be mentioned.
  • the thermoplastic resin may have a crosslinkable group such as an epoxy group, an amino group, a radically polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxy group and an alkoxysilyl group.
  • a crosslinkable group such as an epoxy group, an amino group, a radically polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxy group and an alkoxysilyl group.
  • the specific photosensitive composition may contain a filler.
  • the filler is not particularly limited, but examples include silica-based fillers (quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, ultrafine amorphous silica, etc.), silicon nitride, and silver powder. , alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic fillers such as inorganic balloons, etc.
  • Organic fillers such as epoxy fillers can also be used.
  • the specific photosensitive composition may contain an antioxidant.
  • antioxidants include commonly used antioxidants such as hindered phenol-based antioxidants, citric acid, phosphoric acid, and sulfur-based antioxidants.
  • As the hindered phenol-based antioxidant various ones can be used, including IRGANOX (registered trademark) 1010 available from BASF.
  • IRGANOX registered trademark 1010 available from BASF.
  • sulfur-based antioxidants include mercaptan-based compounds, salts of mercaptan-based compounds, sulfide-based compounds (sulfide carboxylic acid ester-based compounds, etc.), polysulfide-based compounds, dithiocarboxylate-based compounds, thiourea-based compounds, and thiophosphates.
  • antioxidants 1 type may be used and 2 or more types may be used together.
  • the specific photosensitive composition may contain a radical inhibitor.
  • radical inhibitors include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), tetrakis(methylene- Phenolic radical inhibitors such as 3(3,5-di-t-butyl-4-hydroxyphenyl)propionate)methane; phenyl- ⁇ -naphthylamine, ⁇ -naphthylamine, N,N'-sec-butyl-p-phenylene Examples include amine-based radical inhibitors such as diamine, phenothiazine, and N,N'-diphenyl-p-phenylenediamine. Moreover, as these radical inhibitors, 1 type may be used and 2 or more types may be used together.
  • the substrate laminate manufacturing method according to the first embodiment satisfies the following condition 1. It is preferable to satisfy the following condition 2, more preferably to satisfy the following condition 3, and further preferably to satisfy the following condition 3.
  • Condition 1 The reaction rate of the curable compound in the first layer before step Se is 95% or more, and the content of alkaline component in the first layer before step Se is 1000 ppm or less.
  • Condition 2 Condition 1 above is satisfied, and the softening point of the first layer before step Se is 100° C. or higher.
  • Condition 3 The condition 2 above is satisfied, and the elastic modulus of the first layer measured by the nanoindentation test method at a temperature of 100° C. before step Se is 1500 N/mm 2 or more.
  • a substrate laminate according to the second embodiment has a first substrate, a second substrate, and a cured material layer that bonds the first substrate and the second substrate.
  • the cured product layer has, from the first substrate side, a first layer composed of a cured photosensitive composition and a second layer composed of a cured adhesive in this order.
  • the first layer is patterned.
  • the photosensitive composition contains a curable compound having a cationic polymerizable group and a photocationic polymerization initiator, and has alkali solubility.
  • the substrate laminate according to the second embodiment is a substrate laminate obtained by the manufacturing method according to the first embodiment described above. Therefore, in the substrate laminate according to the second embodiment, descriptions of parts overlapping with those described in the first embodiment will be omitted. Since the substrate laminate according to the second embodiment is obtained by the manufacturing method according to the above-described first embodiment, the substrate laminate has excellent adhesion between substrates and is less likely to be contaminated with foreign matter.
  • the substrate laminate according to the second embodiment is prepared as follows. It preferably satisfies condition i, more preferably satisfies condition ii below, further preferably satisfies condition iii below, still more preferably satisfies condition iv below, and particularly preferably satisfies condition v below.
  • Condition i The cured product layer further has a coating layer that covers at least part of the wall surface of the first layer, the coating layer and the second layer are integrally formed, and the wall surface of the second layer is curved.
  • Condition ii Curability that satisfies the above condition i and the photosensitive composition that is the material of the first layer has one or more cationic polymerizable groups selected from the group consisting of glycidyl groups and alicyclic epoxy groups. Contains compounds.
  • Condition iii Condition i above is satisfied, and the first substrate is a glass substrate.
  • Condition iv The adhesive that satisfies condition iii above and is the material of the second layer is an epoxy adhesive.
  • Condition v a polysiloxane that satisfies the condition iv above and the photosensitive composition that is the material of the first layer has one or more cationic polymerizable groups selected from the group consisting of glycidyl groups and alicyclic epoxy groups. Contains compounds.
  • the die shear strength of the substrate laminate according to the second embodiment is preferably 10 kgf or more, more preferably 15 kgf or more.
  • the upper limit of the die shear strength of the substrate laminate according to the second embodiment is not particularly limited, it is, for example, 100 kgf or less.
  • the die shear strength can be measured by the method described in Examples below or a method equivalent thereto.
  • the substrate laminate according to the second embodiment is used, for example, as a member constituting MEMS (Micro Electro Mechanical Systems).
  • the substrate laminate according to the second embodiment is used as a member constituting sensors such as image sensors, acceleration sensors, and pressure sensors.
  • the image sensor having the substrate laminate according to the second embodiment has excellent adhesion between the substrates, but also has problems caused by foreign matter contamination (cracks). occurrence, etc.) can be suppressed.
  • one of the first substrate and the second substrate is a transparent substrate, and the other is a semiconductor element substrate (image sensor substrate).
  • the solution S2 was heated to a temperature of 105° C., and the solution S1 was added dropwise to the solution S2 over 3 hours. After stirring for a minute, a solution S3 was obtained.
  • the reaction rate of the alkenyl group of the compound contained in the obtained solution S3 was measured by 1 H-NMR and found to be 95% or more.
  • the solution S3 was heated to a temperature of 105° C., and the solution S4 was added dropwise to the solution S3 over 1 hour. After stirring for a minute, a solution S5 was obtained.
  • the reaction rate of the alkenyl group of the compound contained in the obtained solution S5 was measured by 1 H-NMR, and the reaction rate was 95% or more.
  • the curable compound P1 has a plurality of cationically polymerizable groups (specifically alicyclic epoxy groups) and a plurality of alkali-soluble groups (specifically X2 groups) in one molecule, and It was a polysiloxane compound (polymer with a weight average molecular weight of 30,000) having a cyclic polysiloxane structure in its chain.
  • the curable compound P2 has a plurality of cationically polymerizable groups (specifically glycidyl groups) and a plurality of alkali-soluble groups (specifically X2 groups) in one molecule, and has a cyclic It was a polysiloxane compound having a polysiloxane structure (polymer having a weight average molecular weight of 28,000).
  • ⁇ Preparation of photosensitive composition> The materials shown in Table 1 were blended in the amounts shown in Table 1 to obtain photosensitive compositions PS1 to PS4 used in Examples and Comparative Examples. When the curable compounds P1 and P2 were blended, they were blended as solution SP1 and solution SP2, respectively. In Table 1, the amount of PGMEA in the photosensitive compositions PS1 and PS2 also includes the amount of PGMEA in the solution SP1 or the solution SP2. Also, in Table 1, "-" means that the material was not blended.
  • Example 1 (Preparation of sample 1) A first lamination in which a photosensitive composition PS1 is applied on a glass substrate as a first substrate by a spin coater, and a coating film (thickness: 50 ⁇ m) composed of the photosensitive composition PS1 is formed on the glass substrate. got stuff The first laminate was then heated for 10 minutes on a hot plate heated to a temperature of 120°C.
  • the exposed first laminate was left in an atmosphere at a temperature of 25°C for 1 minute, and then immersed in an aqueous TMAH solution (TMAH concentration: 2.38% by mass) as an alkaline developer for 60 seconds.
  • TMAH concentration: 2.38% by mass aqueous TMAH solution
  • the first laminate immersed in the alkaline developer was washed with water for 30 seconds, and then the moisture on the surface was removed with compressed air.
  • the first laminate from which moisture has been removed is heated for 30 minutes to cure the patterned coating film (exposed area), thereby forming the film on the glass substrate.
  • a sample 1 having a patterned first layer (a cured layer of a grid-patterned coating) was obtained.
  • sample 2 (Preparation of sample 2) The sample 1 was cut with a dicing machine to obtain a sample 2 that was individualized into a size of 12 mm ⁇ 12 mm. A sample 2 is a sample obtained by dividing the sample 1 into pieces.
  • a second laminate was obtained by laminating Sample 2 and a silicon wafer (size: 12 mm ⁇ 12 mm) as a second substrate via an epoxy adhesive. Note that the layers were laminated so that an epoxy-based adhesive was interposed between the first layer and the silicon wafer.
  • the epoxy adhesive used contains bisphenol A diglycidyl ether as a main agent, contains an imidazole-based curing agent as a curing agent, and has a mass ratio of the main agent and the curing agent (main agent/curing agent) of 100/3. It was a thermosetting adhesive.
  • the substrate laminate of Example 1 was obtained by heating the second laminate in an oven at a temperature of 200°C for 2 hours.
  • the substrate laminate of Example 1 includes a glass substrate, a patterned first layer (a layer composed of a cured photosensitive composition PS1), and a second layer composed of a cured adhesive. , and a silicon wafer were laminated in this order.
  • Example 2 A substrate laminate of Example 2 was obtained in the same manner as in Example 1, except that the photosensitive composition PS2 was used instead of the photosensitive composition PS1. Also for the substrate laminate of Example 2, from the scanning electron microscope image of the cross section, at least a part of the wall surface of the first layer is covered with a coating layer (a layer integrally formed with the second layer). , and that the wall surface of the second layer is a curved surface.
  • a coating layer a layer integrally formed with the second layer.
  • Example 3 A substrate laminate of Example 3 was obtained in the same manner as in Example 1, except that the photosensitive composition PS3 was used instead of the photosensitive composition PS1. Also for the substrate laminate of Example 3, from the scanning electron microscope image of the cross section, at least a part of the wall surface of the first layer is covered with a coating layer (a layer integrally formed with the second layer). , and that the wall surface of the second layer is a curved surface.
  • Example 4 The glass substrate of the second laminate was obtained by using an ultraviolet curable acrylic adhesive ("U-2052Z” manufactured by Chemitec) instead of the epoxy adhesive, and without heating the second laminate.
  • a substrate laminate of Example 4 was obtained in the same manner as in Example 1, except that ultraviolet rays were irradiated from the side to cure the adhesive.
  • the substrate laminate of Example 4 from the scanning electron microscope image of the cross section, at least a part of the wall surface of the first layer is covered with a coating layer (a layer integrally formed with the second layer). , and that the wall surface of the second layer is a curved surface.
  • the exposed first laminate was left in an atmosphere at a temperature of 25°C for 1 minute, and then immersed in an aqueous TMAH solution (TMAH concentration: 2.38% by mass) as an alkaline developer for 60 seconds.
  • TMAH concentration: 2.38% by mass aqueous TMAH solution
  • the first laminate immersed in the alkaline developer was washed with water for 30 seconds, and then the moisture on the surface was removed with compressed air.
  • a sample 1 having a layer in which the coating film was cured in a semi-cured state was obtained.
  • sample 2 (Preparation of sample 2) The sample 1 was cut with a dicing machine to obtain a sample 2 that was individualized into a size of 12 mm ⁇ 12 mm. A sample 2 is a sample obtained by dividing the sample 1 into pieces.
  • a silicon wafer (size: 12 mm x 12 mm) as a second substrate was placed on a hot plate heated to 150°C. Then, Sample 2 was layered on the silicon wafer to obtain a second layered product. In addition, when laminating, the semi-cured layer of the sample 2 was laminated so as to face the silicon wafer. Then, a weight of 1 kg was placed on the second laminate placed on the hot plate for 10 minutes to press the silicon wafer and the glass substrate together. Then, the second laminate after pressure bonding was heated in an oven at a temperature of 200° C. for 2 hours to obtain a substrate laminate of Comparative Example 1.
  • a glass substrate, a layer composed of a patterned cured product (a layer composed of a cured product of photosensitive composition PS1), and a silicon wafer were laminated in this order. It was a substrate laminate having a three-layer structure.
  • Comparative Example 2 A substrate laminate of Comparative Example 2 was obtained in the same manner as in Comparative Example 1, except that the photosensitive composition PS2 was used instead of the photosensitive composition PS1.
  • Comparative Example 3 A substrate laminate of Comparative Example 3 was obtained in the same manner as in Comparative Example 1, except that the photosensitive composition PS3 was used instead of the photosensitive composition PS1.
  • Comparative Example 4 A substrate laminate of Comparative Example 4 was obtained in the same manner as in Example 1, except that the photosensitive composition PS4 was used instead of the photosensitive composition PS1.
  • Comparative Example 5 A substrate laminate of Comparative Example 5 was obtained in the same manner as in Comparative Example 1, except that the photosensitive composition PS4 was used instead of the photosensitive composition PS1.
  • first layer or semi-cured layer may be referred to as a patterned layer.
  • reaction rate (1-second peak area/first peak area) x 100".
  • reaction rate (1-second peak area/first peak area) x 100.
  • the reaction rate obtained here is the reaction rate of the curable compound in the patterned layer before bonding the silicon wafer and the glass substrate together.
  • the "alkaline component (TMAH) content (unit: ppm) in the patterned layer” was calculated from the “amount of the alkaline component (TMAH) contained in the eluate".
  • the content of the alkali component obtained here is the content of the alkali component in the patterned layer before bonding the silicon wafer and the glass substrate together.
  • die shear strength Using a die shear tester ("SERIES 4000” manufactured by Nordson DAGE), a shearing force (more specifically, a shearing force to the glass substrate and the silicon wafer) is applied to the substrate laminate, and when the silicon wafer is peeled off from the substrate laminate was measured. The maximum value of the load was taken as the die shear strength.
  • the die shear strength was measured according to MIL STD 883 under the conditions of a shear height of 50 ⁇ m and a shear speed of 80 ⁇ m/sec. When the die shear strength was 10 kgf or more, it was evaluated as "excellent adhesion between substrates". On the other hand, when the die shear strength was less than 10 kgf, it was evaluated as "not excellent in adhesion between substrates”.
  • Measuring device Dynamic viscoelasticity measuring device (UBM "Rheogel-E4000") Measurement mode: Tension/sine wave control mode Initial load: 300mN Temperature range: -50°C to 200°C Heating rate: 3°C/min Measurement frequency: 1Hz
  • the elastic modulus obtained here is the elastic modulus of the patterned layer before bonding the silicon wafer and the glass substrate together.
  • Detailed measurement conditions are as follows. Measuring device: Nanoindentation tester ("ENT-NEXUS (registered trademark)" manufactured by Elionix) Temperature of sample 2 during measurement (temperature of measurement environment): 100°C Indenter approach speed: 100 nm/sec Maximum load: 3 mN Load application speed: 0.6mN/sec Maximum load holding time: 5sec Unloading speed: 0.6mN/sec Stiffness calculation: When the load is 10% off the maximum load Drift measurement: When the load is 90% off the maximum load
  • the substrate laminate was observed from the glass substrate side with an optical microscope, and if no defects (at least one of cracks and peeling) were confirmed in any of the five substrate laminates, A (excellent reliability It was evaluated as On the other hand, when defects (at least one of cracks and delamination) were confirmed in at least one of the five substrate laminates, it was evaluated as B (not excellent in reliability).
  • High temperature and high humidity storage stability Five substrate laminates were prepared for each example and each comparative example, and each was placed in a constant temperature and humidity chamber ("EC-25MHP" manufactured by Hitachi Global Life Solutions, temperature: 85 ° C., relative humidity: 85%), High temperature and high humidity storage stability was evaluated according to the following criteria. In addition, the confirmation of the foreign material was performed with the optical microscope.
  • D After 200 hours, foreign matter with a maximum diameter of 1 ⁇ m or more was attached to the surface of the glass substrate on the hollow side of at least one of the five substrate laminates.
  • Examples 1 to 4 and Comparative Examples 1 to 5 the type of photosensitive composition used, the presence or absence of the second layer, the type of adhesive used to form the second layer, the reaction rate, the content of the alkali component, Tables 2 and 3 show the evaluation results of patterning property, die shear strength, softening point, elastic modulus, evaluation results of foreign matter contamination prevention performance, evaluation results of reliability by thermal shock test, and evaluation results of high temperature and high humidity storage stability. are shown respectively.
  • the photosensitive compositions used in Examples 1 to 4 contained a curable compound having a cationic polymerizable group and a photocationic polymerization initiator, and had alkali solubility.
  • the patterned layer (the first layer composed of the patterned cured product) and the silicon wafer (second substrate) were sandwiched through the second layer composed of the adhesive cured product. was glued down.
  • the die shear strength was 10 kgf or more. Therefore, the substrate laminates of Examples 1 to 4 were excellent in adhesiveness between substrates.
  • the evaluation result of the contamination prevention performance was A. Therefore, the substrate laminates of Examples 1 to 4 were excellent in preventing contamination by foreign matter.
  • the photosensitive compositions used in Comparative Examples 4 and 5 did not contain a photocationic polymerization initiator.
  • the layer obtained by curing the patterned layer (semi-cured layer) and the silicon wafer (second substrate) were bonded without interposing the second layer.
  • Comparative Examples 4 and 5 As shown in Table 3, in Comparative Examples 4 and 5, the die shear strength was less than 10 kgf. Therefore, the substrate laminates of Comparative Examples 4 and 5 were not excellent in adhesion between substrates. In Comparative Examples 1 to 3 and 5, the evaluation result of foreign matter contamination prevention performance was B. Therefore, the substrate laminates of Comparative Examples 1 to 3 and 5 were not excellent in foreign matter contamination prevention performance.
  • Substrate laminate 11 First substrate 12: Second substrate 13: Cured material layer 131: First layer 132: Second layer 133: Coating layer 300: Coating film 300a: Exposed area 300b: Non-exposed area 301: Photo Mask 400: Adhesive Z: Hollow part

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Abstract

Ce procédé de fabrication d'un empilement de substrats comprend une étape Sa, une étape Sb, une étape Sc, une étape Sd et une étape Se. À l'étape Sa, une composition photosensible est appliquée sur une surface d'un premier substrat (11) pour former un revêtement (300). À l'étape Sb, le revêtement (300) est irradié avec un faisceau d'énergie active à travers un photomasque (301) pour former une partie exposée (300a) composée de la composition photosensible dans un état semi-durci, et une partie non exposée (300b). À l'étape Sc, la partie non exposée (300b) est retirée du premier substrat (11) au moyen d'une solution révélatrice alcaline pour former un revêtement structuré sur le premier substrat (11). À l'étape Sd, le revêtement structuré est chauffé pour obtenir une première couche (131). À l'étape Se, la première couche (131) et un second substrat sont liés ensemble avec un adhésif entre eux, puis l'adhésif est durci pour obtenir une seconde couche.
PCT/JP2022/015716 2021-03-29 2022-03-29 Empilement de substrats, capteur d'image et procédé de fabrication d'un empilement de substrats WO2022210799A1 (fr)

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JP2012018410A (ja) * 2010-06-07 2012-01-26 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、画像表示装置の隔壁の形成方法、画像表示装置の製造方法及び画像表示装置
JP2014053512A (ja) * 2012-09-07 2014-03-20 Nikon Corp 固体撮像装置及びその製造方法
JP2019081342A (ja) * 2017-11-01 2019-05-30 株式会社カネカ 基板積層体、および前記積層体を用いたイメージセンサ
JP2020024984A (ja) * 2018-08-06 2020-02-13 株式会社カネカ チップ接着用ポジ型感光性ダイボンド剤、近紫外線硬化性の基板接着剤及びそれを用いたチップの製造方法

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JP2012018410A (ja) * 2010-06-07 2012-01-26 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、画像表示装置の隔壁の形成方法、画像表示装置の製造方法及び画像表示装置
JP2014053512A (ja) * 2012-09-07 2014-03-20 Nikon Corp 固体撮像装置及びその製造方法
JP2019081342A (ja) * 2017-11-01 2019-05-30 株式会社カネカ 基板積層体、および前記積層体を用いたイメージセンサ
JP2020024984A (ja) * 2018-08-06 2020-02-13 株式会社カネカ チップ接着用ポジ型感光性ダイボンド剤、近紫外線硬化性の基板接着剤及びそれを用いたチップの製造方法

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